The invention relates to a polymerizable composition, a polymer, a resist, and a process for electron beam lithography.
In addition to the development of increasingly fine lithography techniques for wafer structuring, the development of such techniques for mask production is also playing a more and more important role in the production of semiconductor components. For the masks that, as a rule, include a quartz glass substrate with applied chromium layer (CoG: chrome on glass), electron beam lithography is now being used increasingly frequently for structuring the chromium.
For this purpose, the mask is coated with a resist (photoresist) that is then exposed in a targeted manner to an electron beam (i.e. structured) in a mask recorder and then developed. In a subsequent etching step, the chromium on the mask is removed from the parts now no longer protected by the photoresist, and the lithography mask is complete. The problems occurring in the production of the lithography mask are described briefly below.
In spite of a reduction factor of four or five times (4 or 5xc3x97), the structures to be imaged on the masks are now so small that the laser recorders already used to date have to be increasingly replaced by higher-resolution electron beam recorders.
By introducing the OPC (optical proximity correction), auxiliary structures have to be integrated into the mask layout. The structures are substantially smaller than the structural elements to be imaged.
PSM (phase shift mask) technology has particular requirements for mask production since in this case additional layers have to be applied to the mask or the substrate has to be ablated in a defined manner in order to achieve the desired phase jumps. At the same time, there is currently no process for PSM mask production that records both levels by using electron beam lithography mask recorders. The second level has been optically recorded to date. A reason for this is the poor charge conduction in the resist; by recording on the resist by using an electron beam, the mask is negatively charged during the recording process, which is generally referred to as charging.
In phase shift mask production, two separate lithography steps are required, the charging problem occurring in the second step.
In the first step, the chromium layer of the mask is structured, suitable earthing of the mask blank in the mask recorder making it possible to still conduct away the resulting negative electrical charge of the mask without problems.
In the second lithography step, applied resist must be recorded on by using (exposed to) electron beams again, but now on an already incomplete (prestructured) chromium layer. Owing to the interrupted chromium layer, the charge can no longer be conducted away over the whole surface by earthing; the mask blank builds up a negative charge during the recording process. However, this negative charge build-up influences the electron beam, incident on the sample, in the mask recorder, which is required both for recording and for adjustment control. This influence leads to undesired deflection and divergence of the electron beam, which is troublesome particularly during adjustment but also leads to undesired distortions and recording errors during recording of the second lithography plane of the phase shift masks.
Solving the problem of charging with a copolymer blend or a blend of an insulating polymer and a conductive polymer is known from an article by M. A. Z. Hupcey, C. K. Ober (SPIE Vol. 3048, pages 100-104). However, these blends have too low an exposure sensitivity, which leads to an undesired increase in the recording times. Furthermore, the development processes are expensive.
Because the problem is acute in particular for the future 75 nm node, there is at present no fixed potential solution for production. Testing of the use of additional, separate conductive resists in the context of a two-layer system is known. The mask blank is first coated with a commercial structurable Ebeam resist, on which a separate layer of a nonstructurable, conductive organic resist which is intended to serve for the necessary charge removal is applied in a second step. This additional resist layer is then completely detached together with the exposed or unexposed parts of the Ebeam resist in the development process following the structuring, with the result that the mask blank thereafter contains only the desired Ebeam resist structures.
However, in addition to the application of the Ebeam resist, an additional coating step is required. The additional step complicates the overall process. The reason is the very expensive (particles, uniformity, additional undesired process times, delay time, stability problems) and risky coating of mask blanks generally. In contrast to wafer production (round wafers), the square mask blanks are substantially more complicated to coat, and it is for this reason that any additional avoidable coating process is avoided in mask production.
All possible approaches known to date for realizing a conductive resist failed to meet the criteria of the high resolution required and high exposure sensitivity, so that no material which meets the present day and future production requirements has as yet been proposed.
It is accordingly an object of the invention to provide a polymerizable composition, a polymer, a resist, and a process for electron beam lithography that overcome the hereinafore-mentioned disadvantages of the heretofore-known devices of this general type and that solves or at least reduces the charging problem and at the same time has high exposure sensitivity.
With the foregoing and other objects in view, there is provided, in accordance with the invention, a polymerizable composition for use in electron beam lithography. The polymerizable composition has the following structural formula: 
In the formula, m is a first number from 0.1 to 0.9. n is a second number from 0.1 to 0.9 with m+n=1. I is an integer from 1 to 100. R1 is a first substituent that can be H, an alkyl, a halogen, an amine, a silicon compound, or a germanium compound. The first substituent can have a chain length of up to six carbon, silicon, or germanium atoms. R2 is a second substituent that can be H, an alkyl, a halogen, an amine, a silicon compound, or a germanium compound. The second substituent has a chain length of up to six carbon, silicon, or germanium atoms. R3 is an eliminatable organic protective group.
Compared with the two necessary coating processes described in the prior art, it is possible with the polymerizable composition according to the invention to manage with a single coating process. The resulting resist already has the necessary electrical conductivity in addition to easy structurability. The production process is thus substantially simplified and the costs are reduced.
A resist according to the invention is, for example, applied directly to the chromium-structured layer of a lithography mask and thus ensures that charge is optimally conducted away, while the additional conductive resist layer used in the abovementioned prior art permits no contact of the chromium but can only remove the surface charge. With the resist according to the invention, charge can thus be better conducted away.
Other features that are considered as characteristic for the invention are set forth in the appended claims.
Although the invention is illustrated and described herein as embodied in a polymerizable composition, a polymer, a resist, and a process for electron beam lithography, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.